AU1669399A

AU1669399A - Extrusion process for enhancing the melt strength of polypropylene

Info

Publication number: AU1669399A
Application number: AU16693/99A
Authority: AU
Inventors: Bart Fischer; Andreas Herman Hogt; Geesje Klasina Spijkerman
Original assignee: Akzo Nobel NV
Current assignee: Akzo Nobel NV
Priority date: 1997-11-21
Filing date: 1998-11-04
Publication date: 1999-06-15
Anticipated expiration: 2018-11-04
Also published as: CN1279700A; IL136242A; JP2001524565A; NO20002586L; CN1174036C; BG104453A; RU2205190C2; AU751755B2; IL136242A0; ZA9810274B; TR200001396T2; DE69836145T2; CA2310743A1; ES2273443T3; BR9814682A; EP1034213A1; US6323289B1; WO1999027007A1; PT1034213E; KR100606013B1

Abstract

The invention relates to a process for enhancing the melt strength of polypropylene comprising the steps of:mixing the polypropylene with at least one peroxydicarbonate;reacting said polypropylene and peroxydicarbonate at a temperature between 150° C. and 300° C., with the proviso that the peroxydicarbonate is not in the form of an aqueous dispersion.

Description

WO 99/27007 PCT/EP98/07219 1 EXTRUSION PROCESS FOR ENHANCING THE MELT STRENGTH OF POLYPROPYLENE 5 The invention pertains to a process for enhancing the melt strength of a polypropylene by mixing a peroxydicarbonate with the polypropylene and heating the polypropylene/peroxydicarbonate mixture. 10 Such a process is known from EP-B-0 384 431. This reference describes a process for preparing polypropylene (PP) with a branching index of less than 1 comprising (1) mixing a low decomposition temperature peroxide, such as a peroxydicarbonate, with the PP, (2) heating or maintaining the resulting 15 mixture at a temperature from room temperature up to 120 0 C, and then (3) heating the PP at a temperature of 130 to 150 0 C to deactivate substantially all the free radicals present in said PP. The obtained PP has a significant amount of long chain branches and has an increased weight average molecular weight giving the polymer a significant strain hardening elongational 20 viscosity. It is mentioned that in step (3) the heating may be done by extrusion or in a fluidized bed. It is further stated that at a temperature above 120 0 C an essentially linear polymer with little or no branching is obtained. Apparently, the significant strain hardening elongational viscosity is related to 25 an improved melt strength of the obtained PP due to long chain branching. It is only mentioned in this publication that step (3) of this process can be performed by extrusion, in the examples the entire process is carried out in a sealed reaction vessel. A disadvantage of this process is that it comprises three steps, which is undesirable in practice. 30 DE-A-4340194 (US 5,416,169) describes a process for preparing PP having a high melt strength and a chain branching coefficient of 1, by mixing bis(2 ethylhexyl)peroxydicarbonate with a linear, crystalline PP, followed by heating WO 99/27007 PCT/EP98/07219 2 at 70 to 1500C. In a subsequent step, the PP is taken out of the reaction vessel and is melt-kneaded. The peroxydicarbonate may be dissolved in an inert solvent before it is added to the PP. It is stated that other peroxydicarbonates, having a similar decomposition temperature, cannot be 5 used for this purpose. A disadvantage of this process is that it can only be performed using one specific peroxide, i.e., bis(2-ethylhexyl)peroxydicarbonate. Another drawback is that the process is performed in two steps, which is undesirable and 10 uneconomical in practice. It is the object of the present invention to provide a process which does not have the above-mentioned drawbacks and which process yields PP having a good melt strength. 15 To this end, the present invention provides a process for enhancing the melt strength of polypropylene comprising the steps of: - mixing the polypropylene with at least one peroxydicarbonate; - reacting said polypropylene and peroxydicarbonate at a 20 temperature between 1500C and 3000C, with the proviso that the peroxydicarbonate is not in the form of an aqueous dispersion in a polar medium with at least 90% by weight of the initiator particles being smaller than 50pm and at least 99% by weight of the initiator particles being smaller than 65pm. Preferably, the reaction conditions are chosen such that more 25 than 50% by weight, more preferably more than 70% by weight, and most preferably, more than 80 % by weight of the peroxide is still present when the mixture of peroxide and polymer reaches a temperature of 1200C, more preferably 1500C. 30 In the non-prepublished patent application now published as WO 97/49759 a process for enhancing the melt strength of a polypropylene is described, WO 99/27007 PCT/EP98/07219 3 wherein a dispersion of an initiator, such as a peroxydicarbonate, in a polar medium, e.g., water, and with a particular particle size distribution, is contacted with the polypropylene and the resulting mixture is heated. This process may be carried out using an extruder. 5 The process according to the present invention is a process providing PP having an enhanced melt strength. Since the processing of PP frequently involves extrusion of the PP, either for pelletization in case of storage and transport or for further processing, i.e., the formation of an end product, it is a 10 further advantage that the invention process is an extrusion process, allowing the modification of the PP, to enhance the melt strength, to be combined with said processing step. The term "polypropylene" ("PP") refers to polymers or mixtures of polymers 15 containing at least 50% by weight of polymerized propylene. Polymerization catalysts may be Ziegler-Natta, metallocene or other types giving stereospecific polymerization of propylene. Use may be made in this connection of homopolymers of propylene; random, alternating, or block copolymers; or random, alternating, or block terpolymers of propylene and 20 another olefin. Generally, a propylene copolymer or terpolymer will contain one or more other olefins, such as ethylene, butene, pentene, hexene, heptene, or octene, but it may also comprise other olefinically unsaturated monomers or combinations of these, such as acrylates, styrene, styrene derivatives, acrylonitrile, vinyl acetate, vinylidene chloride, and vinyl chloride. 25 It is preferred here to restrict the content of olefins other than propylene to 30% by weight of the copolymer. Especially suited to be used are homopolymers of propylene, copolymers of propylene and ethylene or mixtures of polypropylene and polyethylene containing not more than 10% by weight of polymerized ethylene. 30 The melting point of normally solid commercially available PP is about 160- WO 99/27007 PCT/EP98/07219 4 1700C. The melting point of propylene copolymers and tercopolymers in general can be lower. The process of the invention preferably is carried out at a temperature in the range of from 150 to 3000C, more preferably from 160 to 2500C, and most preferably from 170 to 2250C. 5 The molecular weight of the PP used can be selected from a wide range. Indicative of the molecular weight is the melt flow index (MFI). Use may be made of a PP having a MFI from 0.1 to 1000 g/10min (2300C, 21.6 N). Preferably, use is made of a PP having a MFI from 0.5 to 250 g/10min. 10 The process according to the present invention is suitably carried out in melt mixing equipment known to a person skilled in the art. Preferably, an extruder or a kneader is used. More preferably, use is made of a single or twin screw extruder. An internal mixer such as a Banbury mixer optionally coupled to an 15 extruder may also be used. The peroxydicarbonate may be mixed first with the PP and then the mixture may be extruded. Alternatively, the peroxydicarbonate may be added to the extruder already containing the PP by injection or spraying, or may be added 20 together with the PP. It is preferred to introduce a solid peroxydicarbonate together with the PP into the extruder, for example, by using a feeder. The temperature setting of the extruder should allow the PP to melt, i.e. above 1500C. The screw speed typically is from about 25 to 500 rpm. 25 Normal residence time in the extruder is 15 sec. - 30 min. The longer residence times can be achieved by using additional static mixers etc. The extruded strand may be further processed as known to one of ordinary skill in the art. Normally, the extruded strand is fed through a water bath and 30 granulated using a granulator. Alternatively, the extruded modified PP is formed directly into a desired end product.

WO 99/27007 PCT/EP98/07219 5 It is preferred to carry out the process of the present invention in an atmosphere of an inert gas, such as nitrogen or argon. Preferably, nitrogen is used. 5 Solid as well as liquid peroxydicarbonates may be used in the process according to the present invention. A solution of a peroxydicarbonate in an inert solvent, such as isododecane, or in the form of frozen flakes, may also be used. Suitable inert solvents are known to one skilled in the art. It is 10 preferred to use a solid peroxydicarbonate, in the form of, for example, flakes, finely divided particles (powder), or a liquid peroxydicarbonate, optionally adsorbed on or absorbed in a suitable carrier, such as silica or polypropylene powder or pellets. The use of a solid peroxydicarbonate permits a higher storage and processing temperature. Such higher temperature is beneficial 15 when the peroxydicarbonate is to be introduced into an extruder using (loss in-weight) feeders. The peroxydicarbonates used in the process of the present invention have a half life of one hour at temperatures around 650C. 20 Suitable examples of peroxydicarbonates have the formula the formula

R

1

-OC(O)OOC(O)O-R

2 , wherein R 1 and R 2 are independently selected from the group consisting of CH 3 , 2-i-C 3

H

7 0-C 6

H

4 , C 2

HCH(CH

3 ), 4-CH 3

-C

6

H

4 , CI3CC(CH 3

)

2 , 0 7

H

15 , c-C 6

HI

1

CH

2 , 3-t-C 4

H

9

-C

6 H, C13Si(CH 2

)

3 , 0 6

H

5 , 25 CH 3

CH(OCH

3

)CH

2

CH

2 , C 6

H

5 0CH 2

CH

2 , C 6

H

5

CH

2 , Z-C 8

H

1 7

CH=CH(CH

2

)

8 , 2

CH

3

-C

6

H

4 , (CH 3

)

2

CHCH

2

CH(CH

3 ), 3,4-di-CH 3

-C

6

H

3 , 013C, CHCH(CI), CICH 2 , [C2H 5 0C(O)] 2

CH(CH

3 ), 3,5-di-CH 3 -- CH 3 , C 8 1, 7 , C 2

H

5 , 018H37, 2-oxo-1,3 dioxolan-4-CH 2 , C 2

H

5

CH(CI)CH

2 , 4-CH30-CeH64, i-C 4

H

9 , CH 3 SO2CH 2

CH

2 ,

C

1 2

H

25 , 6

H

5

CH(CI)CH

2 , H 2 C=CHC(0)OCH 2 CH2, 4-NO2-C 6

H

4 , C 4

H

9 , C 10

H

21 , 30 C 4

HCH(C

2

H

5

)CH

2 , H 2

C=CHCH

2 , 2-Cl-c-C 6 Ho 10 , H 2

C=C(CH

3

)CH

2 , c-0 6 H,,

CICH

2

CH

2 , 4-[C 6

H

5

-N=N]-C

6

H

4

CH

2 , C16H33, 1-naphtyl, 4-t-C 4

H

9

-C

6 Ho 10 , 2,4,5-tri- WO 99/27007 PCT/EP98/07219 6

CI-C

6

H

2 , CI(CH 2

)

3 , C 14

H

29 , 9-fluorenyl, 4-NO2-C 6

H

4

CH

2 , 2-i-C 3

H

7

-C

6

H

4 ,

CH

3 0CH 2

CH

2 , H 2

C=C(CH

3 ), 3-CH 3

-C

6

H

4 , BrCH 2

CH

2 , 3-CH 3 -5-i-C 3

H

7

-C

6

H

3 , Br 3

CCH

2 , C2HsOCH 2

CH

2 , 4-CH 3 0C(O)-CH 4 , H 2 C=CH, i-C 3

H

7 , 2-C 2

H

5

CH(CH

3

)

C

6

H

4 , CI3CCH 2 , C 5

H

11 , c-C 1 2

H

23 , 4-t-C 4

H,-C

6

H

4 , C 6 H13, C3H7, CH 3 0CH 2

CH

2 , 5 C 6

H

1 3

CH(CH

3 ), CH 3 0C(CH 3

)

2

CH

2

CH

2 , C 3 H70CH 2

CH

2 , CH 3 0CH 2

CH(CH

3 ), 2-i

C

3

H

7 -5-CH 3 -c-C 6

H

9 , C 4

H

9 0CH 2

CH

2 , t-C 4 H,, (CH 3 )3CCH 2 , wherein i = iso, t = tertiary, Z = cis, and c = cyclic. More preferred are bis(4-tert butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, and dimyristyl peroxydicarbonate, which peroxides are solid at room temperature, and 10 diisopropylperoxydicarbonate, di-n-butylperoxydicarbonate and bis(2 ethylhexyl)peroxydicarbonate, which are liquid at room temperature, either pure or as a solution in isododecane. Optionally, a combination of peroxydicarbonates or peroxydicarbonates and other peroxides may be employed in order to influence the melt flow index of the (co)polymer and/or 15 enhance the degree of modification of the (co)polymer. The quantity of peroxydicarbonate to be used will be dependent on the desired degree of PP modification and on the PP employed. Preferably, use is made of peroxydicarbonate concentrations in the range of 0.1 to 10 meq 20 (=milliequivalents=millimoles of peroxide) per 100 g PP, more preferably in the range of 0.25 to 5 meq/100 g PP. In another embodiment of the present invention, the modification process is carried out in the presence of a coagent in order to influence the melt flow 25 index of the (co)polymer and/or enhance the degree of modification of the (co)polymer. A coagent is generally understood to be a polyfunctional reactive additive such as a polyunsaturated compound which will react rapidly with polymer 30 radicals, will overcome steric hindrance effects and minimize undesirable side reactions. Further information about coagents is set forth in Rubber Chemistry WO 99/27007 PCT/EP98/07219 7 and Technology, Vol. 61, pp. 238-254 and W. Hofmann, Progress in Rubber and Plastics Technology, Vol. 1, No. 2, March 1985, pp. 18-50. The term "coagent" has the same meaning as given in these publications. 5 A wide variety of useful coagents are commercially available including di- and triallyl compounds, di- and tri(meth)acrylate compounds, bismaleimide compounds, divinyl benzene, 1,3-diisopropenylbenzene and its oligomer, vinyl toluene, vinyl pyridine, parachinone dioxime, 1,2-cis-polybutadiene and their derivatives. Particularly preferred coagents include triallyl cyanurate, triallyl 10 isocyanurate, ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate. The incorporation of an effective amount of one or more of these coagents into the (co)polymer, prior to or during the reaction with the present tend to 15 influence the melt flow index and molecular weight of the modified (co)polymer. Although the process of the present invention can be carried out as a batch internal mixer (Banbury) process, preferably it is performed as a continuous 20 process. The PP obtained using the process according to the present invention may be processed into an end product without any further adaptations if so desired. The modified PP can be processed into the desired end product in all kinds of 25 ways known to the skilled person, with the processing conditions generally being dependent on the material and equipment employed. Optionally, the modified PP may be purified, modified or moulded, in one or more process steps, prior to its final processing. Thus, there may be further 30 modification using another polymer or monomer in order to enhance the end product's compatibility with other materials.

WO 99/27007 PCT/EP98/07219 8 Alternatively, the modified PP may be degraded or, on the contrary, crosslinked slightly, to increase its processability and/or applicability. 5 Generally, to achieve the desired end conventional adjuvants, in an amount known to one skilled in the art, such as antioxidants, UV-stabilizers, lubricants, antidegradants, foaming agents, nucleating agents, fillers, pigments and/or antistatic agents are added to the PP. These adjuvants can be added to the PP before as well as during or after the modifying step 10 according to the invention. For example, a blowing agent can be added or gas can be injected into the extruder before, during or after the modification, in order to produce foamed PP. Preferably, a stabilizer, e.g., one or more antioxidants, is added in order to render harmless any free radicals still present in the obtained PP as well as any radicals which may be formed later 15 from unreacted peroxide and/or subsequent processing under air/oxygen. In a typical experiment from 0.01 to 1.0 parts per hundred parts of PP of an antioxidant are used. The PP obtained by the invention process does not show a substantial 20 difference in weight average molecular weight. Only peroxydicarbonates have been found to give the desired enhanced melt strength in the process of the present invention. Diacyl peroxides and peresters did not give such improvement in PP melt strength. While not wishing to be bound by any particular it is believed that the improvement in melt strength is caused by 25 modification of the PP due to the formation of alkylcarbonate-polymer adducts, with the alkylcarbonate groups originating from the peroxydicarbonate used. The PP obtained by the process according to the present invention may be 30 further processed, for example, by foaming, foam moulding, extrusion, injection moulding, blow moulding, extrusion coating, profile extrusion, or WO 99/27007 PCT/EP98/07219 9 thermoforming. The modification reaction with peroxide may also be performed during such processing. The invention is illustrated by the following examples. 5 Experimental The following materials and methods are employed in the examples: 10 Polypropylene : Hostalen® PPN 1042 copolymer of polypropylene (granules), ex Hoechst Novolen® 3200HX random polypropylene (granules), ex BASF Peroxides: 15 Trigonox® EHP-C75 solution of 75% bis(2-ethylhexyl)peroxydicarbonate in isododecane, ex Akzo Nobel Trigonox NBP-C50 solution of 50% dibutyl peroxydicarbonate in isododecane, ex Akzo Nobel Perkadox® 16 bis(4-tert-butylcyclohexyl) peroxydicarbonate 20 (pure), ex Akzo Nobel Perkadox 26 dimyristyl peroxydicarbonate (pure), ex Akzo Nobel Liladox® 90 P dicetyl peroxydicarbonate (90%), ex Akzo Nobel Miscellaneous: 25 Perkalink® 300 triallyl cyanurate (coagent), ex Akzo Nobel Irganox® 1010 antioxidant, ex Ciba Geigy PROCEDURE A Mixing procedure: 30 The proper amount of the peroxydicarbonate and the antioxidant were added to 300 g of polypropylene powder in a 3 liter bucket and tumble-mixed by WO 99/27007 PCTIEP98/07219 10 hand for 5 minutes at room temperature. Compounds were extruded immediately after mixing. Compounding procedure: 5 All compounds were melt-modified by extrusion in a Haake "TW100" twin screw extruder with intensive mixing screws attached to a Haake "Rheocord System 40". During the experiment nitrogen was passed in counterflow from the hopper up through the feeder. 10 The extruder comprised a barrel housing four consecutive temperature chambers, wherein the first chamber had a temperature of 170 0 C the second 180 0 C, the third 180 0 C and the fourth chamber 190 0 C. The screw speed was 50 rpm. The extruded strand was fed through a water bath and granulated with an 15 Automatic "ASG5" granulator.

WO 99/27007 PCT/EP98/07219 11 PROCEDURE B Modification procedure Modification experiments were carried out in a Buchi 150 ml RVS laboratory autoclave ('special', type BEP280). 5 The initiator was diluted to 33% with isododecane and Primol® 352. The autoclave was filled with 50 grams of polymer/anti-oxidant mixture and after closing, flushed with nitrogen (3 bar) followed by vacuum sucking (3 times) to avoid the presence of oxygen. 10 Then, the autoclave was heated up (continuous nitrogen flow, anchor stirrer speed: 150 rpm). At a polymer temperature of 1550C (measured by means of a PT100 thermocouple, directly into the polymer), the proper amount of peroxide/solvent was injected into the autoclave. The autoclave was further 15 heated up to 2300C during 5 minutes. The reaction mixture was molten after approximately 15 minutes (total experimental time) as measured by torque increase. Then the reaction mixture was removed, cooled and granulated. PROCEDURE C 20 The proper amount of the peroxydicarbonate and the antioxidant were added to polypropylene homopolymer powder and tumble-mixed at room temperature. This mixture was blended with the PP homopolymer powder and dosed to the extruder or dosed separately together with the PP copolymer granules. 25 All compounds were melt-modified by extrusion in a Werner & Pfleiderer ZSK 30 twin screw extruder. The extruder comprised of a barrel housing with four consecutive temperature 30 chambers, wherein the first chamber had a temperature of 100 0 C, the second and third 1800C and the fourth chamber 1900C.

WO 99/27007 PCT/EP98/07219 12 The compounds were fed into the first chamber of the extruder. During the experiment nitrogen was passed in counterflow from the hopper up through the feeder. The screw speed was 200 rpm. 5 The extruded strand was fed through a water bath and granulated with an "Automatic ASG5" granulator. Test procedures: MFI (Melt Flow Index), characterizing the flow behaviour of a PP melt, was 10 measured with a G6ttfert Melt Indexer (model MP-D) according to DIN 53735 and ASTM 1238 (2300C, 21.6 N load). Die swell, i.e. the degree to which the extrudate swells in a direction perpendicular to the direction of extrusion after it leaves the die, due to the 15 elasticity of the PP melt, was determined by measuring the thickness of the strand coming out of the Melt Indexer and subtracting the nozzle diameter (2.1 mm) and is the mean value of ten measurements in mm. In the evaluation of the modified polypropylene the die swell was usually found to be proportional to the melt strength. 20 Melt strength, i.e. the ability of a melt of PP to withstand a tensile elongation or stretching without breaking, was measured using a Gbttfert Rheotens attached to a Gbttfert Rheograph 2001 capillary rheometer (1900C, speed 0.5 mm/s, acceleration 24 mm/s2, strand length 70 mm). 25 In Tables 1 and 2, data on Comparative Examples A-G, preparation of PP without using a peroxydicarbonate, and Examples 1-17 according to the process of the present invention are presented (comparative examples C and D are controls with solvent without peroxide). The amounts of peroxide used 30 are expressed as milliequivalents (mmol peroxide groups) of peroxide per hundred gram of PP (meq/100 g PP).

WO 99/27007 PCT/EP98/07219 13 The examples show an increased die swell and melt strength as compared with PP prepared without using a peroxydicarbonate. 5 The increased die swell is always related to the improvement of the elastic viscosity and melt strength. In Table 2 data on homo-PP, co-PP and random-PP examples are shown as obtained following procedure C (examples 15 - 17, Comparative Examples F 10 G) In procedure C, where a Werner & Pfleiderer ZSK 30 twin screw extruder is used, a PP extrusion process on production scale was simulated where within 30 seconds residence time the compounds are melt-modified. During the 15 extrusion process the temperature of the compound increases from approximately 20 0 C (hopper) to approximately 1900C at the end of the extruder. In this process the peroxydicarbonate decomposes according to the Arrhenius equation dependent on the temperature and residence times in the different temperature chambers of the extruder. 20 Arrhenius equation : Kd = A. e

-E

a/RT where Kd = the rate constant for the dissociation in s -1 A = the Arrhenius frequency factor in s

-

1 (for Liladox 90P: 3.02E+15) 25 Ea =the activation energy for the peroxydicarbonate in J/mole (for Liladox 90P: 124.3E+3) R = 8.3142 J/mole.K T = the temperature in K 30 The concentration of the initiator at any time can be calculated from the equation: WO 99/27007 PCT/EP98/07219 14 [I] = [10]. e -Kd t where [10] = the original initiator concentration 5 [I] = the initiator concentration at time t t = the time in seconds Table 3 shows the amount of reacted peroxydicarbonate as a function of the temperature and residence time in the extruder as calculated by using the 10 above equations. The compound temperature is taken as the mean temperature of the barrel temperature and a linear temperature profile (200C to 1900C in 30 seconds). In this procedure more than 80 %w/w of the peroxydicarbonate reacts with the 15 PP above 1200C. Therefore the enhancement of the melt strength of PP, as a result of the reaction of peroxydicarbonate with PP, in an extrusion process mainly takes place above 12000. The invention is not limited to the above description, the requested rights are 20 rather determined by the following claims.

WO 99/27007 15PCT/EP98/0721 9 C) CD (0~ CON- LO* C) CD C \J c'J 0) C0 r- '-C C)) C)U' (0 (0- CD)-( o ~ C) C:) U6 0 0 0 0 U- 0) 0 I 0) C\J 0 Q0U' mo 7 C)r-L 0) C) j C C ) 0)l N 00 . C))c CL x '-0 'ci co mo 6f cn 0C010 E -- a) toL- L L.. ~. . .E > or 0- C- ) CCuI cu a) CU) E -a0 0 (n' N 0Y 0) U)~~5U = D U C L - >< 0 0 c -Dx- x 0 - ~ c~< 0C XV: l Cu 0)1 0) -0-h Cu x0O - N- a) 0LUU - W0- H0 0 EL - L0-. - - WO 99/27007 16PCTIEP98/0721 9 L16 ui ~ ~ U (D0 CjC 0 f LO (o fl0) 0)- ) NJ 0- _ _ _ ____ C) co lIn UJ 0f ) 0)6O-N 0 00 0 C)C CD) UJ~C)

.-

r )( -e C; C) CL 0a) C) C)L U) C: x a a aa aaaa C) E U) M: Z c)c ca 0 l- a C)C ~ a) C)'- 4 C ) c ~ -- 0 0)~ 0U)n CL 01 c D 0 0U a) 0- (M -:a W ~ E a- 0 ) a U ? a c-W E a) . ~ ~ c C0) a) a o x CL 0 V.52 WO 99/27007 17 PCT/EP98/0721 9 0 ~ 0 m 0 ) 00C)C a, t5-.~ X CU w a_ a) 1E a, a) a)) o -n CD (D C: a a) (D E- a), E, -C)m) CD - L 0 a, .2 00 as E a, (Do a, E w m m w m m ) a -0 '- L- x- ' 00 a), E 0~ U) 0 a, C ) () o- aV a, OC OOO ~0 E aa

Claims

3. Process according to claim 1 or 2, wherein the process is conducted in an extruder. 20
4. Process according to claim 2, wherein the temperature is from 160 to 2500C.
5. Process according to claim 4, wherein the temperature is from 170 to 25 2250C.
6. Process according to any of the preceding claims, wherein the peroxide comprises a peroxycarbonate. 30 7. Process according to any of the previous claims, wherein the peroxydicarbonate has the formula R 1 -OC(O)OOC(O)O-R 2 , wherein R 1 and R 2 are independently selected from the group consisting of CH 3 , 2-i C 3 H 7 0-CH 4 , C 2 H 5 CH(CH 3 ), 4-CH 3 -C 6 H 4 , C3CC(CH 3 ) 2 , C 7 Hs 15 , c-0 6 H 11 CH 2 , WO 99/27007 PCT/EP98/07219 19 3-t-C 4 H 9 -C 6 H, CI 3 Si(CH 2 ) 3 , C 6 H 5 , CH 3 CH(OCH 3 )CH 2 CH 2 , C 6 H 5 0CH 2 CH 2 , C 6 H 5 CH 2 , Z-C 8 H 17 CH=CH(CH 2 ) 8 , 2-CH 3 -C 6 H 4 , (CH 3 ) 2 CHCH 2 CH(CH 3 ), 3,4 di-CH 3 -C 6 H 3 , C13C, CHCH(CI), CICH 2 , [C 2 H 5 0sC(O)] 2 CH(CH 3 ), 3,5-di-CH 3 C 6 H 3 , C 8 H 1 7 , C 2 H 5 , C 1 8 H 37 , 2-oxo-1,3-dioxolan-4-CH 2 , C 2 H 5 CH(CI)CH 2 , 4 5 CH30-C 6 H 4 , i-C 4 H 9 , CH 3 SO 2 CH 2 CH 2 , C 12 H 25 , C 6 H 5 CH(CI)CH 2 , H 2 C=CHC(O)OCH 2 CH 2 , 4-NO2-C 6 H 4 , C 4 H 9 , C 10 H 21 , C 4 H 9 CH(C 2 H)CH 2 , H 2 C=CHCH 2 , 2-Cl-c-C6Hio, H 2 C=C(CH 3 )CH 2 , c-C 6 H 11 , CICH 2 CH 2 , 4-[C 6 H 5 N=N]-C 6 H 4 CH 2 , C 16 H 33 , 1-naphtyl, 4-t-C 4 H 9 -C 6 H 1 0 , 2,4,5-tri-C-C 6 H 2 , CI(CH 2 ) 3 , C 14 H 2 9 , 9-fluorenyl, 4-NO2-C6H 4 CH 2 , 2-i-03H7-C6H4, 10 CH 3 0CH 2 CH 2 , H 2 C=C(CH 3 ), 3-CH 3 -C 6 H 4 , BrCH 2 CH2, 3-CH 3 -5-i-C 3 H 7 Ce 6 H 3 , Br 3 CCH 2 , C 2 H 5 0sCH 2 CH 2 , 4-CH 3 0C(O)-C 6 H 4 , H 2 C=CH, i-C 3 H 7 , 2 C 2 H 5 CH(CH 3 )-C 6 H 4 , CI3CCH 2 , C 5 H 11 , c-C 1 2 H 2 3 , 4-t-C 4 H 9 -C 6 H4, 06H13, C 3 H 7 , CH 3 OCH 2 CH 2 , C 6 Hi 3 CH(CH 3 ), CH 3 0C(CH 3 ) 2 CH 2 CH 2 , C 3 H 7 0CH 2 CH 2 , CH 3 0CH 2 CH(CH 3 ), 2-i-C 3 H 7 -5-CH 3 -c-C 6 H 9 , C 4 H 9 0CH 2 CH 2 , t-C 4 H 9 , 15 (CH 3 ) 3 CCH 2 , wherein i = iso, t = tertiary, Z = cis, and c = cyclic.
8. Process according to claim 7, wherein R1 and R2 are independently selected from the group consisting of CH 3 , C 6 HsOCH 2 CH 2 , 4-t-C 4 H 9 20 C 6 Ho 10 , C 16 H 3 3 , (CH 3 ) 3 CH 2 CH(CH 3 )CH 2 CH 2 , C 13 H 3 7 , C 4 H 9 , c-C 6 H, CH 3 CH(OCH 3 )CH 2 CH 2 , C 3 H 7 , i-C3H 7 /C 2 H 5 CH(CH 3 ), C 10 H 2 1 , C25, C 14 H 29 , C 2 H 5 CH(CH 3 ), C 6 HCH 2 , C 18 H 3 z 7 and C 4 H 9 CH(C 2 H,)CH 2 .
9. Process according to claim 8, wherein the peroxydicarbonate is selected 25 from the group consisting of bis(4-tert-butylcyclohexyl) peroxy dicarbonate, dicetyl peroxydicarbonate, and dimyristyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-n-butylperoxy dicarbonate, di-sec-butylperoxydicarbonate, bis(2 ethylhexyl)peroxydicarbonate. 30
10. Process according to any of the claims 7-9, wherein the peroxydicarbonate is a liquid or preferably a solid at room temperature. WO 99/27007 PCTIEP98/07219 20
11. Process according to claim 10, wherein the liquid is a solution of the peroxydicarbonate in an inert solvent, and is preferably bis(2 ethylhexyl)peroxydicarbonate or dibutyl peroxydicarbonate in 5 isododecane.
12. Process according to any one of the preceding claims wherein at least one coagent is present in the reaction mixture when the polypropylene is reacted with the peroxydicarbonate. 10
13. Polypropylene having an enhanced melt strength obtainable using the process according to any one of the preceding claims.
14. Process for producing an extruded, melt spun or blown, moulded, 15 thermoformed or foamed material based on a polypropylene, wherein use is made of polypropylene according to claim 13.